CN113329876A - Outer packaging material for electricity storage device, method for producing outer packaging material for electricity storage device, and electricity storage device - Google Patents
Outer packaging material for electricity storage device, method for producing outer packaging material for electricity storage device, and electricity storage device Download PDFInfo
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- CN113329876A CN113329876A CN202080010644.2A CN202080010644A CN113329876A CN 113329876 A CN113329876 A CN 113329876A CN 202080010644 A CN202080010644 A CN 202080010644A CN 113329876 A CN113329876 A CN 113329876A
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- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/78—Cases; Housings; Encapsulations; Mountings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides an outer packaging material for an electricity storage device, which can maintain high adhesion of a barrier layer having a corrosion-resistant coating even in the case of an electrolyte adhering thereto, and which has excellent moldability. The outer packaging material for a power storage device is composed of a laminate comprising at least a first base material layer, a first adhesive layer, a second base material layer, a second adhesive layer, a barrier layer, and a heat-fusible resin layer in this order, and is provided on the upper surface of the laminateAt least one side of the barrier layer has a corrosion-resistant coating film, and when the corrosion-resistant coating film is analyzed by time-of-flight secondary ion mass spectrometry, the corrosion-resistant coating film is derived from PO3 ‑Peak intensity P ofPO3Relative to that derived from CrPO4 ‑Peak intensity P ofCrPO4Ratio PPO3/CrPO4In the range of 6 to 120.
Description
Technical Field
The present invention relates to an outer package for an electric storage device, a method for manufacturing the outer package for an electric storage device, and an electric storage device.
Background
Currently, various types of power storage devices have been developed. In these electric storage devices, electric storage device elements composed of electrodes, electrolytes, and the like need to be sealed with an outer packaging material or the like. A metal outer packaging material is often used as an outer packaging material for an electric storage device.
In recent years, with the enhancement of performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, cellular phones, and the like, electric storage devices having various shapes have been demanded. Further, reduction in thickness and weight of the power storage device is also required. However, it is difficult for conventional metal outer packaging materials to conform to the diversification of the shape of the electric storage device. Further, since the outer package is made of metal, there is a limit to the reduction in weight of the outer package.
For this reason, an outer cover for an electric storage device, which can be easily processed into various shapes and can be made thinner and lighter, has been proposed, and is a film-shaped laminate in which a base layer, a barrier layer, and a heat-fusible resin layer are sequentially laminated (see, for example, patent document 1).
In such a film-shaped outer covering material for an electric storage device, a concave portion is generally formed by molding, an electric storage device element such as an electrode or an electrolyte is disposed in a space formed by the concave portion, and the heat-fusible resin layers are heat-fused to each other, whereby an electric storage device in which the electric storage device element is housed is obtained.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2008-287971
Disclosure of Invention
Technical problem to be solved by the invention
When moisture enters the inside of the electric storage device, the moisture reacts with an electrolyte or the like, and an acidic substance may be generated. For example, an electrolytic solution used in a lithium ion power storage device or the like contains a fluorine compound (LiPF) as an electrolyte6、LiBF4Etc.), it is known that fluorine compounds generate hydrogen fluoride when reacted with water.
The barrier layer of the outer packaging material for an electricity storage device formed of a film-like laminate is generally formed of a metal foil or the like, and there is a problem that the barrier layer is easily corroded when it comes into contact with an acid. As a technique for improving the corrosion resistance of such an outer covering material for an electric storage device, a technique is known in which a barrier layer having a corrosion-resistant coating film formed on the surface thereof is surface-treated by a chemical method.
Various chemical surface treatments for forming a corrosion-resistant coating have been known, such as chromate treatment using a chromium compound such as chromium oxide, and phosphoric acid treatment using a phosphoric acid compound.
However, the inventors of the present invention have made extensive studies and found that the adhesion between a conventional barrier layer having a corrosion-resistant coating and a layer adjacent to the side on which the corrosion-resistant coating is provided (i.e., the adhesion between the corrosion-resistant coating and the layer in contact therewith at the interface) is insufficient. More specifically, when the electrolyte adheres to the outer covering material for the electric storage device, high adhesion between the corrosion-resistant coating and the layer in contact therewith may not be maintained.
As described above, the outer packaging material for an electric storage device is used for molding, and therefore high moldability is required.
Under such circumstances, a main object of the present invention is to provide an outer packaging material for an electric storage device, which can maintain high adhesion of a barrier layer having a corrosion-resistant coating film even when an electrolyte adheres thereto, and which has excellent moldability. Further, another object of the present invention is to provide a method for producing the outer package for an electric storage device and an electric storage device using the outer package for an electric storage device.
Technical solution for solving technical problem
The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, it has been found that an exterior material for an electricity storage device, which comprises a laminate comprising at least a first base material layer, a first adhesive layer, a second base material layer, a second adhesive layer, a barrier layer, and a heat-sealable resin layer in this order, has excellent moldability while maintaining high adhesion even when an electrolyte solution is adhered to the surface of the barrier layer, has a corrosion-resistant coating film on at least one surface of the barrier layer, and is derived from PO when the corrosion-resistant coating film is analyzed by time-of-flight secondary ion mass spectrometry3 -Peak intensity P ofPO3Relative to that derived from CrPO4 -Peak intensity P ofCrPO4Ratio PPO3/CrPO4In the range of 6 to 120.
The present invention has been completed based on these findings and further through repeated research.
That is, the present invention provides the following embodiments.
An outer packaging material for a power storage device, comprising a laminate comprising at least a first base material layer, a first adhesive layer, a second base material layer, a second adhesive layer, a barrier layer and a heat-fusible resin layer in this order,
a corrosion-resistant coating film on at least one surface of the barrier layer,
when the corrosion-resistant coating is analyzed by time-of-flight secondary ion mass spectrometry, the corrosion-resistant coating is derived from PO3 -Peak intensity P ofPO3Relative to that derived from CrPO4 -Peak intensity P ofCrPO4Ratio PPO3/CrPO4In the range of 6 to 120.
Effects of the invention
According to the present invention, it is possible to provide an outer packaging material for an electric storage device, which can maintain high adhesion of a barrier layer having a corrosion-resistant coating film even when an electrolytic solution is adhered thereto, and which has excellent moldability. Further, the present invention can provide a method for producing the outer cover for electric storage device, and an electric storage device using the outer cover for electric storage device.
Drawings
Fig. 1 is a schematic diagram showing an example of a cross-sectional structure of an outer packaging material for an electric storage device according to the present invention.
Fig. 2 is a schematic diagram showing an example of a cross-sectional structure of an outer packaging material for an electric storage device according to the present invention.
Fig. 3 is a schematic diagram showing an example of a cross-sectional structure of an outer packaging material for an electric storage device according to the present invention.
Fig. 4 is a schematic diagram showing an example of a cross-sectional structure of an outer packaging material for an electric storage device according to the present invention.
Detailed Description
The outer packaging material for an electric storage device of the present invention is characterized by comprising a laminate comprising at least a first base material layer, a first adhesive layer, a second base material layer, a second adhesive layer, a barrier layer, and a heat-fusible resin layer in this order, wherein at least one side of the barrier layer has a corrosion-resistant coating film, and when the corrosion-resistant coating film is analyzed by time-of-flight secondary ion mass spectrometry, the PO-derived material is derived from PO3 -Peak intensity P ofPO3Relative to that derived from CrPO4 -Peak intensity P ofCrPO4Ratio PPO3/CrPO4In the range of 6 to 120. The followingThe outer packaging material for power storage devices of the present invention and a power storage device using the outer packaging material for power storage devices will be described in detail.
In the present specification, the numerical ranges indicated by "to" mean "above" and "below". For example, the expression of 2 to 15mm means 2mm to 15 mm.
1. Laminated structure of outer packaging material for electricity storage device
As shown in fig. 1, the outer cover for an electric storage device of the present invention is composed of a laminate including at least a first base material layer 11, a first adhesive layer 21, a second base material layer 12, a second adhesive layer 22, a barrier layer 3, and a heat-fusible resin layer 4 in this order. In the outer covering material for an electric storage device of the present invention, the first base material layer 11 is the outermost layer side, and the heat-fusible resin layer 4 is the innermost layer. That is, at the time of assembling the electric storage device, the heat-fusible resin layers 4 located at the edges of the electric storage device element are heat-fused to each other to seal the electric storage device element, thereby sealing the electric storage device element.
As shown in fig. 3 and 4, the outer covering material for an electric storage device of the present invention may be provided with an adhesive layer 5 as needed between the barrier layer 3 and the heat-fusible resin layer 4 for the purpose of improving the adhesion therebetween. As shown in fig. 4, a surface coating layer 6 or the like may be provided on the outer side of the first base material layer 11 (the side opposite to the heat-fusible resin layer 4 side), as needed.
The barrier layer 3 has a corrosion-resistant coating on at least one surface thereof. The corrosion-resistant coating contains chromium. Fig. 1 is a schematic diagram showing a case where the outer covering for an electric storage device of the present invention has a corrosion-resistant film 3a on the surface of the barrier layer 3 on the side of the heat-fusible resin layer 4. Fig. 2 to 4 schematically illustrate a case where the outer covering for an electric storage device of the present invention has corrosion-resistant films 3a and 3b on both surfaces of the barrier layer 3. As will be described later, the outer packaging material for an electric storage device according to the present invention may have the corrosion-resistant film 3a only on the surface of the barrier layer 3 on the side of the heat-fusible resin layer 4, may have the corrosion-resistant film 3b only on the surface of the barrier layer 3 on the side of the second base material layer 12, and may have the corrosion-resistant films 3a and 3b on both surfaces of the barrier layer 3.
The thickness of the laminate constituting the outer covering 10 for an electric storage device is not particularly limited, but the upper limit is preferably about 180 μm or less, about 155 μm or less, and about 120 μm or less from the viewpoint of cost reduction, energy density improvement, and the like, and the lower limit is preferably about 35 μm or more, about 45 μm or more, and about 60 μm or more from the viewpoint of maintaining the function of the outer covering for an electric storage device that protects the electric storage device elements, and preferable ranges are, for example, about 35 to 180 μm, about 35 to 155 μm, about 35 to 120 μm, about 45 to 180 μm, about 45 to 155 μm, about 45 to 120 μm, about 60 to 180 μm, about 60 to 155 μm, and about 60 to 120 μm, and particularly preferable range is about 60 to 180 μm.
In the outer packaging material for an electricity storage device, MD and TD in the manufacturing process of the barrier layer 3 described later can be generally distinguished. For example, when the barrier layer 3 is made of an aluminum alloy foil, linear streaks called Rolling marks are formed on the surface of the aluminum alloy foil in the Rolling Direction (RD: Rolling Direction) of the aluminum alloy foil. Since the rolling marks extend in the rolling direction, the rolling direction of the aluminum alloy foil can be grasped by observing the surface of the aluminum alloy foil. In addition, in the production process of the laminate, since the MD of the laminate generally coincides with the RD of the aluminum alloy foil, the MD of the laminate can be determined by observing the surface of the aluminum alloy foil of the laminate and determining the Rolling Direction (RD) of the aluminum alloy foil. Further, since the TD of the laminate is the direction perpendicular to the MD of the laminate, the TD of the laminate can also be determined.
2. Composition of layers forming outer packaging material for electricity storage device
[ first base material layer 11 and second base material layer 12]
In the outer packaging material for power storage devices of the present invention, the first base material layer 11 and the second base material layer 12 are layers provided for the purpose of, for example, exhibiting a function as a base material of the outer packaging material for power storage devices. The first base material layer 11 is a layer located on the outermost layer side of the outer packaging material for power storage devices. The second base material layer 12 is a layer provided between the first base material layer 11 and the barrier layer 3 with a first adhesive layer 21 described later interposed therebetween.
The material for forming the first base material layer 11 and the second base material layer 12 is not particularly limited as long as it can function as a base material, that is, has at least an insulating property. The first base material layer 11 and the second base material layer 12 can be formed using, for example, a resin, and the resin may contain additives described later.
When the first base material layer 11 and the second base material layer 12 are each formed of a resin, the first base material layer 11 and the second base material layer 12 may each be a resin film formed of a resin, for example, or may be a layer formed by applying a resin. The resin film may be an unstretched film or a stretched film. Examples of the stretched film include a uniaxially stretched film and a biaxially stretched film, and a biaxially stretched film is preferable. Examples of the stretching method for forming the biaxially stretched film include sequential biaxial stretching, blow molding, simultaneous biaxial stretching, and the like. Examples of the method for applying the resin include roll coating, gravure coating, and extrusion coating.
Examples of the resin forming the first substrate layer 11 and the second substrate layer 12 include resins such as polyester, polyamide, polyolefin, epoxy resin, acrylic resin, fluorine resin, polyurethane, silicone resin, and phenol resin, and modified products of these resins. The resins forming the first base material layer 11 and the second base material layer 12 may be copolymers of these resins, or may be modified products of the copolymers. Further, a mixture of these resins is also possible.
As the resin forming the first base material layer 11 and the second base material layer 12, polyester and polyamide are preferably used, respectively.
Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and a copolyester. The copolyester may be a copolyester containing ethylene terephthalate as a main repeating unit. Specifically, copolymer polyesters obtained by polymerizing ethylene terephthalate as a main repeating unit with ethylene isophthalate (hereinafter, abbreviated as polyethylene glycol (terephthalate/isophthalate)), polyethylene glycol (terephthalate/adipate), polyethylene glycol (terephthalate/sodium sulfoisophthalate), polyethylene glycol (terephthalate/sodium isophthalate), polyethylene glycol (terephthalate/phenyl dicarboxylate), polyethylene glycol (terephthalate/decane dicarboxylate), and the like can be mentioned. These polyesters may be used alone in 1 kind, or 2 or more kinds may be used in combination.
Specific examples of the polyamide include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and copolymers of nylon 6 and nylon 66; a hexamethylenediamine-isophthalic acid copolyamide such as nylon 6I, nylon 6T, nylon 6IT, and nylon 6I6T (I represents isophthalic acid and T represents terephthalic acid) and a polyamide (MXD6 (poly-m-xylylene adipamide) and other aromatic-containing polyamides, a polyamide PACM6 (poly-bis (4-aminocyclohexyl) methane adipamide) and other alicyclic polyamides comprising a structural unit derived from terephthalic acid and/or isophthalic acid, a polyamide amide copolymer and/or a polyether ester amide copolymer of a copolyamide and a polyester and/or a polyalkylene ether glycol obtained by copolymerizing a lactam component and an isocyanate component such as 4, 4' -diphenylmethane-diisocyanate, and the like, and a polyamide such as a copolymer of these polyamides and/or a polyether ester amide copolymer, and 1 of these polyamides may be used alone, more than 2 kinds may be used in combination.
The first substrate layer 11 and the second substrate layer 12 each preferably contain at least one of polyamide and polyester. From the viewpoint of further improving moldability, it is more preferable that the first substrate layer 11 contains at least one of polyamide and polyester and the second substrate layer 12 contains polyamide, and it is particularly preferable that the first substrate layer 11 and the second substrate layer 12 contain polyamide, and it is more preferable that the first substrate layer 11 and the second substrate layer 12 are composed of polyamide.
The first substrate layer 11 and the second substrate layer 12 preferably each contain at least 1 of a polyester film, a polyamide film, and a polyolefin film, preferably at least 1 of a stretched polyester film, a stretched polyamide film, and a stretched polyolefin film, more preferably at least 1 of a stretched polyethylene terephthalate film, a stretched polybutylene terephthalate film, a stretched nylon film, and a stretched polypropylene film, and further preferably at least 1 of a biaxially stretched polyethylene terephthalate film, a biaxially stretched polybutylene terephthalate film, a biaxially stretched nylon film, and a biaxially stretched polypropylene film.
Specific examples of the combination of the first base material layer 11 and the second base material layer 12 include a polyester film and a nylon film, a nylon film and a nylon film, and a polyester film, and more preferably include a stretched nylon film and a stretched polyester film, a stretched nylon film and a stretched nylon film, and a stretched polyester film. In addition, in these combinations, the polyester film is preferably a polyethylene terephthalate film.
Further, additives such as a lubricant, a flame retardant, an antiblocking agent, an antioxidant, a light stabilizer, a thickener, and an antistatic agent may be present on at least one of the surface and the inside of the first base material layer 11 and the second base material layer 12. The additive may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
In the present invention, it is preferable that a lubricant be present on the surface of the first base material layer 11 in order to improve the moldability of the outer packaging material for an electric storage device. The lubricant is not particularly limited, and preferably an amide-based lubricant is used. Specific examples of the amide-based lubricant include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylol amides, saturated fatty acid diamides, unsaturated fatty acid diamides, fatty acid ester amides, and aromatic diamides. Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and hydroxystearic acid amide. Specific examples of the unsaturated fatty acid amide include oleamide and erucamide. Specific examples of the substituted amide include N-oleoyl palmitamide, N-stearyl stearamide, N-stearyl oleamide, N-oleoyl stearamide, and N-stearyl erucamide. Specific examples of the methylolamide include methylolstearic acid amide. Specific examples of the saturated fatty acid diamide include methylene distearic acid amide, ethylene bisdecanoic acid amide, ethylene dilauric acid amide, ethylene distearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, hexamethylene distearic acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N '-distearyl adipic acid amide, and N, N' -distearyl sebacic acid amide. Specific examples of the unsaturated fatty acid diamide include ethylenedioleamide, ethylenediorucamide, hexamethylenedioleamide, N '-dioleoyl adipic acid amide, N' -dioleoyl sebacic acid amide, and the like. Specific examples of the fatty acid ester amide include stearamide ethyl stearate. Specific examples of the aromatic diamide include xylylene distearamide, xylylene dihydroxystearic amide, and N, N' -distearyl isophthalic amide. The number of the lubricants may be 1 or more.
When the lubricant is present on the surface of the first base material layer 11, the amount of the lubricant present is not particularly limited, but is preferably about 3mg/m2More preferably 4 to 15mg/m2About, more preferably 5 to 14mg/m2Left and right.
The lubricant present on the surface of the first base material layer 11 may be a bleed-out lubricant contained in the resin constituting the first base material layer 11, or may be a lubricant applied to the surface of the first base material layer 11.
In the present invention, from the viewpoint of making the outer packaging material for an electric storage device thin and improving moldability, the thickness of the first base material layer 11 is preferably about 10 μm or more, more preferably about 12 μm or more, and is preferably about 20 μm or less, more preferably about 18 μm or less, more preferably about 15 μm or less, and preferable ranges are about 10 to 20 μm, about 10 to 18 μm, about 10 to 15 μm, about 12 to 20 μm, about 12 to 18 μm, and about 12 to 15 μm. From the same viewpoint, the thickness of the second base material layer 12 is preferably about 12 μm or more, more preferably about 15 μm or more, and is preferably about 30 μm or less, more preferably about 28 μm or less, more preferably about 25 μm or less, and preferable ranges are about 12 to 30 μm, about 12 to 28 μm, about 12 to 25 μm, about 15 to 30 μm, about 15 to 28 μm, and about 15 to 25 μm.
From the same viewpoint, the total thickness of the first base material layer 11 and the second base material layer 12 may be preferably about 20 μm or more, more preferably about 25 μm or more, and still more preferably about 28 μm or more, and may be preferably about 50 μm or less, more preferably about 45 μm or less, more preferably about 40 μm or less, and still more preferably about 35 μm or less, and preferable ranges thereof may be about 20 to 50 μm, about 20 to 45 μm, about 20 to 40 μm, about 20 to 35 μm, about 25 to 50 μm, about 25 to 45 μm, about 25 to 40 μm, about 25 to 35 μm, about 28 to 50 μm, about 28 to 45 μm, about 28 to 40 μm, and about 28 to 35 μm.
In the outer packaging material for an electricity storage device of the present invention, the second adhesive layer 22 described later may have a layer other than the first base material layer 11, the first adhesive layer 21, and the second base material layer 12 on the side opposite to the barrier layer 3 (outer layer side). The material for forming the other layer is not particularly limited as long as it has insulation properties. Examples of the material for forming the other layer include polyester, polyamide, epoxy resin, acrylic resin, fluororesin, polyurethane, silicon-containing resin, phenol resin, polyetherimide, polyimide, and a mixture or copolymer thereof. When another layer is provided, the thickness of the other layer is preferably about 0.1 to 20 μm, more preferably about 0.5 to 10 μm.
[ first adhesive layer 21]
In the outer cover for an electricity storage device of the present invention, the first adhesive layer 21 is a layer provided for bonding the first base material layer 11 and the second base material layer 12.
In the outer covering material for an electric storage device of the present invention, the hardness of the first adhesive layer 21 and the hardness of the second adhesive layer 22, which will be described later, are each preferably 20MPa or more. As a result, the outer packaging material for an electricity storage device, in which the base material layer is formed of a plurality of layers (i.e., the first base material layer 11 and the second base material layer 12), can exhibit particularly excellent moldability. More specifically, when the hardness of the first adhesive layer 21 and the second adhesive layer 22 measured by the nanoindentation method is 20MPa or more, particularly excellent moldability can be exhibited.
From the viewpoint of improving the formability of the outer covering material for an electric storage device, the hardness of the first adhesive layer 21 is more preferably 30MPa or more, still more preferably 51MPa or more, and further preferably 400MPa or less, and still more preferably 350MPa or less. Preferable ranges of the hardness of the first adhesive layer 21 include about 20 to 400MPa, about 20 to 350MPa, about 30 to 400MPa, about 30 to 350MPa, about 51 to 400MPa, and about 51 to 350 MPa.
In the present invention, the hardness of the first adhesive layer 21 and the second adhesive layer 22 measured by the nanoindentation method is a value measured in the following manner. As an apparatus, a nanoindenter ("TriboInducer TI 950" manufactured by Haesi corporation) was used as a indenter of the nanoindenter, and a Berkovich indenter (triangular pyramid) was used, and with respect to the hardness of the second adhesive layer 22, the indenter was pressed against the surface (the surface exposed to the second adhesive layer 22, in the direction perpendicular to the lamination direction of the layers) of the second adhesive layer 22 of the outer packaging material for an electric storage device in an environment with a relative humidity of 50% and 23 ℃ for 10 seconds, the indenter was pressed into the adhesive layer from the surface until the load reached 40 μ N, the state was maintained for 5 seconds, and thereafter, the load was removed for 10 seconds, and the maximum load P was usedmax(μ N) projected area of contact A (μm) at maximum depth2) From PmaxThe indentation hardness (MPa) was calculated. The hardness of the first adhesive layer 21 was measured in the same manner as the second adhesive layer 22, except that the load was set to 10 μ N.
The hardness of the first adhesive layer 21 can be adjusted to the above-mentioned value not only by adjusting the kind of the resin contained in the adhesive but also by adjusting the molecular weight of the resin and/or the number of crosslinking points, the ratio of the main agent to the curing agent, the dilution ratio of the main agent to the curing agent, the drying temperature, the curing time, and the like.
The adhesive used to form the first adhesive layer 21 is not limited, but may be any of a chemical reaction type, a solvent volatilization type, a hot melt type, a hot press type, and the like. The adhesive may be a 2-liquid curable adhesive (2-liquid adhesive), a 1-liquid curable adhesive (1-liquid adhesive), or a resin that does not involve a curing reaction. The first adhesive layer 21 may be a single layer or a plurality of layers.
Specific examples of the adhesive component contained in the first adhesive layer 21 include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolyester; a polyether; a polyurethane; an epoxy resin; a phenolic resin; polyamides such as nylon 6, nylon 66, nylon 12, and copolyamide; polyolefin resins such as polyolefin, cyclic polyolefin, acid-modified polyolefin, and acid-modified cyclic polyolefin; polyvinyl acetate; cellulose; (meth) acrylic resins; a polyimide; a polycarbonate; amino resins such as urea resins and melamine resins; rubbers such as chloroprene rubber, nitrile rubber, and styrene-butadiene rubber; silicone resins, and the like. These adhesive components can be used alone in 1, or can be used in combination of 2 or more. Among these adhesive components, a polyurethane adhesive is preferably used. These adhesive components can be used alone in 1, or can be used in combination of 2 or more. Among these adhesive components, a polyurethane adhesive is preferably used. In addition, when an appropriate curing agent is used together with the resin serving as the adhesive component, the adhesive strength can be improved. The curing agent may be selected from polyisocyanates, polyfunctional epoxy resins, oxazoline group-containing polymers, polyamine resins, acid anhydrides, and the like, as appropriate in accordance with the functional group of the adhesive component.
The urethane adhesive includes, for example, a main agent containing a polyol compound and a curing agent containing an isocyanate compound. Preferred examples of the two-pack curable polyurethane adhesive include two-pack curable polyurethane adhesives containing a polyol such as a polyester polyol, a polyether polyol and an acrylic polyol as a main component and an aromatic or aliphatic polyisocyanate as a curing agent. In addition, as the polyol compound, a polyester polyol having a hydroxyl group in a side chain in addition to a hydroxyl group at the terminal of the repeating unit is preferably used. By forming the first adhesive layer 21 with a urethane adhesive, excellent electrolyte resistance can be provided to the outer packaging material for an electric storage device, and peeling of the first base material layer 11 can be suppressed even when an electrolyte adheres to the side surfaces.
In addition, other components may be allowed to be added to the first adhesive layer 21 within limits that do not interfere with adhesiveness, and colorants, thermoplastic elastomers, tackifiers, fillers, and the like may be contained. By containing a colorant in the first adhesive layer 21, the outer covering material for an electric storage device can be colored. As the colorant, known substances such as pigments and dyes can be used. The colorant may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
The type of the pigment is not particularly limited as long as the adhesiveness of the first adhesive layer 21 is not impaired. Examples of the organic pigment include azo pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, indigo thioindigo pigments, perinone pigments, isoindoline pigments, and benzimidazolone pigments, examples of the inorganic pigment include carbon black pigments, titanium oxide pigments, cadmium pigments, lead pigments, chromium oxide pigments, and iron pigments, and fine powders of Mica (Mica) and fish scale foils.
Among the colorants, carbon black is preferable in order to make the appearance of the outer packaging material for an electricity storage device black, for example.
The average particle size of the pigment is not particularly limited, and may be, for example, about 0.05 to 5 μm, preferably about 0.08 to 2 μm. The average particle diameter of the pigment is a median diameter measured by a laser diffraction/scattering particle size distribution measuring apparatus.
The content of the pigment in the first adhesive layer 21 is not particularly limited as long as it colors the outer packaging material for an electricity storage device, and may be, for example, about 5 to 60 mass%, preferably 10 to 40 mass%.
The thickness of the first adhesive layer 21 is preferably 5 μm or less, and is preferably about 1 to 5 μm, from the viewpoint of making the outer packaging material for an electric storage device thin and improving moldability.
[ second adhesive layer 22]
In the outer packaging material for a power storage device of the present invention, the second adhesive layer 22 is a layer provided for bonding the second base material layer 12 and the barrier layer 3.
As described above, in the outer covering material for an electric storage device according to the present invention, the hardness of the first adhesive layer 21 and the hardness of the second adhesive layer 22 are each preferably 20MPa or more. As a result, the outer packaging material for an electricity storage device, in which the base material layer is formed of a plurality of layers (i.e., the first base material layer 11 and the second base material layer 12), can exhibit particularly excellent moldability. More specifically, when the hardness of the first adhesive layer 21 and the second adhesive layer 22 measured by the nanoindentation method is 20MPa or more, particularly excellent moldability can be exhibited.
From the viewpoint of further improving the formability of the outer covering material for an electric storage device, the hardness of the second adhesive layer 22 is more preferably 30MPa or more, still more preferably 51MPa or more, and further preferably 400MPa or less, and still more preferably 350MPa or less. Preferable ranges of the hardness of the second adhesive layer 22 include about 20 to 400MPa, about 20 to 350MPa, about 30 to 400MPa, about 30 to 350MPa, about 51 to 400MPa, and about 51 to 350 MPa.
In the present invention, the hardness of the second adhesive layer 22 measured by the nanoindentation method is a value measured by the above-described method.
The hardness of the second adhesive layer 22 can be adjusted to the above-mentioned value not only by adjusting the kind of resin contained in the adhesive, but also by adjusting the molecular weight of the resin and/or the number of crosslinking points, the ratio of the main agent to the curing agent, the dilution ratio of the main agent to the curing agent, the drying temperature, the curing time, and the like, as in the case of the first adhesive layer 21.
The adhesive used to form the second adhesive layer 22 is not particularly limited as long as it can provide the second adhesive layer 22 with the above hardness, and the same adhesive as in the first adhesive layer 21 can be exemplified. That is, as a specific example of the adhesive component and the adhesive agent that can be used to form the second adhesive layer 22, the same ones as those in the first adhesive layer 21 described above can be exemplified.
The second adhesive layer 22 may contain a colorant, a thermoplastic elastomer, a tackifier, a filler, and the like. By containing a colorant in the second adhesive layer 22, the outer covering material for an electric storage device can be colored. As the colorant, known substances such as pigments and dyes can be used. The colorant may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
Among the colorants, carbon black is preferable in order to make the appearance of the outer packaging material for an electricity storage device black, for example.
The average particle size of the pigment is not particularly limited, and may be, for example, about 0.05 to 5 μm, preferably about 0.08 to 2 μm. The average particle diameter of the pigment is a median diameter measured by a laser diffraction/scattering particle size distribution measuring apparatus.
The content of the pigment in the second adhesive layer 22 is not particularly limited as long as it colors the outer packaging material for an electricity storage device, and may be, for example, about 5 to 60 mass%, preferably 10 to 40 mass%.
The thickness of the second adhesive layer 22 is preferably 5 μm or less, and may be preferably about 1 to 5 μm, from the viewpoint of making the outer packaging material for an electric storage device thin and improving moldability.
[ coloring layer ]
The colored layer is, for example, a layer (not shown) provided between the second base material layer 12 and the barrier layer 3 as needed. The colored layer may be provided between the second base material layer 12 and the second adhesive layer 22, or between the second adhesive layer 22 and the barrier layer 3. Further, a colored layer may be provided outside the second base material layer 12. By providing the coloring layer, the outer packaging material for the electric storage device can be colored.
The colored layer can be formed by, for example, applying ink containing a colorant to the surface of the second base material layer 12, the surface of the barrier layer 3, or the like. As the colorant, known substances such as pigments and dyes can be used. The colorant may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
As a specific example of the coloring agent contained in the colored layer, the same ones as those exemplified in the column of [ first adhesive layer 21] can be exemplified.
[ Barrier layer 3]
In the outer packaging material for an electricity storage device, the barrier layer 3 is a layer that at least inhibits the ingress of moisture.
Examples of the barrier layer 3 include a metal foil having barrier properties, a vapor deposited film, and a resin layer. Examples of the vapor deposited film include a metal vapor deposited film, an inorganic oxide vapor deposited film, a carbon-containing inorganic oxide vapor deposited film, and the like, and examples of the resin layer include a fluorine-containing resin such as a polymer mainly composed of polyvinylidene chloride and Chlorotrifluoroethylene (CTFE), a polymer mainly composed of Tetrafluoroethylene (TFE), a polymer having a fluoroalkyl group, and a polymer mainly composed of a fluorocarbon unit, and an ethylene vinyl alcohol copolymer. Further, as the barrier layer 3, a resin film provided with at least 1 of these vapor deposited film and resin layer may be mentioned. The barrier layer 3 may be provided in multiple layers. The barrier layer 3 preferably includes a layer made of a metal material. Specific examples of the metal material constituting the barrier layer 3 include aluminum alloy, stainless steel, titanium steel, and steel sheet, and when used as a metal foil, at least one of aluminum alloy foil and stainless steel foil is preferably contained.
The aluminum alloy foil is more preferably a soft aluminum alloy foil made of, for example, an aluminum alloy subjected to annealing treatment from the viewpoint of improving the formability of the outer packaging material for an electrical storage device, and is preferably an iron-containing aluminum alloy foil from the viewpoint of further improving the formability. The iron content in the iron-containing aluminum alloy foil (100 mass%) is preferably 0.1 to 9.0 mass%, more preferably 0.5 to 2.0 mass%. When the iron content is 0.1 mass% or more, an outer packaging material for an electricity storage device having more excellent moldability can be obtained. By setting the iron content to 9.0 mass% or less, an outer packaging material for an electric storage device having more excellent flexibility can be obtained. Examples of the soft aluminum alloy foil include those having a chemical composition of JIS H4160: 1994A8021H-O, JIS H4160: 1994A8079H-O, JIS H4000: 2014A8021P-O, or JIS H4000: 2014A 8079P-O. Further, silicon, magnesium, copper, manganese, and the like may be added as necessary. The softening can be performed by annealing or the like.
Examples of the stainless steel foil include austenitic, ferritic, austenitic-ferritic, martensitic, and precipitation hardening stainless steel foils. The stainless steel foil is preferably made of austenitic stainless steel from the viewpoint of providing an outer packaging material for an electrical storage device having further excellent formability.
Specific examples of austenitic stainless steel constituting the stainless steel foil include SUS304, SUS301, and SUS316L, and among these, SUS304 is particularly preferable.
The thickness of the barrier layer 3 is not particularly limited as long as it functions as a barrier layer that at least suppresses the penetration of moisture in the case of a metal foil, and may be, for example, about 9 to 200 μm. The thickness of the barrier layer 3 is preferably about 85 μm or less, more preferably about 50 μm or less, still more preferably about 40 μm or less, and particularly preferably about 35 μm or less at the upper limit thereof, and is preferably about 10 μm or more, more preferably about 20 μm or more, and still more preferably about 25 μm or more at the lower limit thereof, and the preferred ranges of the thickness are about 10 to 85 μm, about 10 to 50 μm, about 10 to 40 μm, about 10 to 35 μm, about 20 to 85 μm, about 20 to 50 μm, about 20 to 40 μm, about 20 to 35 μm, about 25 to 85 μm, about 25 to 50 μm, about 25 to 40 μm, and about 25 to 35 μm, of these, about 25 to 50 μm is preferable, and about 25 to 40 μm is particularly preferable. When the barrier layer 3 is made of an aluminum alloy foil, the above range is particularly preferable. In particular, when the barrier layer 3 is made of a stainless steel foil, the thickness of the stainless steel foil is preferably about 60 μm or less, more preferably about 50 μm or less, still more preferably about 40 μm or less, further more preferably about 30 μm or less, particularly preferably about 25 μm or less, as an upper limit, about 10 μm or more, more preferably about 15 μm or more, as a lower limit, and about 10 to 60 μm, about 10 to 50 μm, about 10 to 40 μm, about 10 to 30 μm, about 10 to 25 μm, about 15 to 60 μm, about 15 to 50 μm, about 15 to 40 μm, about 15 to 30 μm, and about 15 to 25 μm, as a preferable thickness range.
[ Corrosion-resistant coatings 3a and 3b ]
In the outer packaging material for an electricity storage device of the present invention, a corrosion-resistant coating film is provided on at least one surface of the barrier layer 3. In the outer packaging material for an electric storage device of the present invention, the corrosion-resistant film 3a may be provided only on the surface of the barrier layer 3 on the side of the heat-fusible resin layer 4, the corrosion-resistant film 3b may be provided only on the surface of the barrier layer 3 on the side of the second base material layer 12, and the corrosion-resistant films 3a and 3b may be provided on both surfaces of the barrier layer 3.
The outer packaging material for an electric storage device according to the present invention is characterized by being derived from PO when the corrosion-resistant coating is analyzed by time-of-flight secondary ion mass spectrometry3 -Peak intensity P ofPO3Relative to that derived from CrPO4 -Peak intensity P ofCrPO4Ratio PPO3/CrPO4In the range of 6 to 120. When the peak intensity ratio is within such a specific range, the barrier layer 3 has excellent adhesion to the layer adjacent to the side on which the corrosion-resistant coating film is provided, even when the electrolyte adheres to the outer covering material for an electric storage device.
When the barrier layer 3 has the corrosion-resistant films 3a and 3b on both surfaces thereof, the peak intensity ratio P of the corrosion-resistant film on either surface is defined as PPO3/CrPO4Within the above range, the peak intensity ratio P is preferable for either of the corrosion resistant films 3a and 3bPO3/CrPO4All within the above range. Particularly, the corrosion-resistant film on the side of the heat-fusible resin layer of the barrier layer and the layer adjacent thereto (for example, provided as required)Adhesive layer, heat-fusible resin layer, etc.) because the adhesion is likely to be lowered by permeation of the electrolyte solution, in the outer covering material for an electric storage device of the present invention, the barrier layer 3 preferably has a corrosion-resistant film 3a on at least the surface of the heat-fusible resin layer 4 side, and the above-mentioned peak intensity ratio P of the corrosion-resistant film 3a is preferably higherPO3/CrPO4Within the above range. These aspects are also similar to the respective peak intensity ratios shown below.
In the present invention, derived from PO3 -Peak intensity P ofPO3Relative to that derived from CrPO4 -Peak intensity P ofCrPO4Ratio PPO3/CrPO4In the range of 6 to 120, the ratio P is preferably selected from the viewpoint of further improving the adhesion of the barrier layer having a corrosion-resistant coating filmPO3/CrPO4The lower limit is about 10 or more, and the upper limit is preferably about 115 or less, more preferably about 110 or less, and still more preferably about 50 or less. In addition, as the ratio PPO3/CrPO4Preferable ranges of (A) include about 6 to 115, about 6 to 110, about 6 to 50, about 10 to 120, about 10 to 115, about 10 to 110, and about 10 to 50.
The corrosion-resistant films 3a and 3b are analyzed by time-of-flight secondary ion mass spectrometry, and specifically, the analysis can be performed under the following measurement conditions by using a time-of-flight secondary ion mass spectrometer.
(measurement conditions)
1, secondary ion: bi-charged ions (Bi) of bismuth clusters3 ++)
1-order ion acceleration voltage: 30kV
Mass range (m/z): 0 to 1500
Measurement range: 100 μm × 100 μm
Scanning number: 16 scans/cycles (scan/cycle)
Number of pixels (1 side): 256pixel
Etching ions: ar gas cluster ion beam (Ar-GCIB)
Etching ion acceleration voltage: 5.0kV
Whether or not the corrosion-resistant coating contains chromium can be confirmed by X-ray photoelectron spectroscopy. Specifically, first, the layers (adhesive layer, heat-fusible resin layer, adhesive layer, etc.) laminated on the barrier layer are physically peeled off from the outer covering for an electricity storage device. Next, the barrier layer was put into an electric furnace, and organic components present on the surface of the barrier layer were removed at about 300 ℃ for about 30 minutes. Then, whether or not chromium is contained is confirmed by using X-ray photoelectron spectroscopy of the surface of the barrier layer.
The corrosion-resistant films 3a and 3b can be formed by chemically surface-treating the surface of the barrier layer 3 with a treatment liquid containing a chromium compound such as chromium oxide.
As the chemical surface treatment using the treatment liquid containing a chromium compound, for example, a method of forming a corrosion-resistant coating on the surface of the barrier layer 3 by applying a treatment liquid in which a chromium compound such as chromium oxide is dispersed in phosphoric acid and/or a salt thereof to the surface of the barrier layer 3 and performing a sintering treatment can be cited.
Peak intensity ratio P of corrosion resistant films 3a, 3bPO3/CrPO4The composition of the treatment liquid for forming the corrosion-resistant films 3a and 3b, and the production conditions such as the temperature and time of the sintering treatment after the treatment can be adjusted.
The ratio of the chromium compound, phosphoric acid and/or a salt thereof in the treatment liquid containing the chromium compound is not particularly limited, and the peak intensity ratio P is set so thatPO3/CrPO4From the viewpoint of setting the amount within the above range, the amount of the phosphoric acid and/or its salt is preferably about 30 to 120 parts by mass, more preferably about 40 to 110 parts by mass, based on 100 parts by mass of the chromium compound. As phosphoric acid and salts thereof, for example, condensed phosphoric acid and salts thereof can also be used.
The treatment liquid containing a chromium compound may further contain an anionic polymer and a crosslinking agent for crosslinking the anionic polymer. Examples of the anionic polymer include poly (meth) acrylic acid or a salt thereof, and a copolymer containing (meth) acrylic acid or a salt thereof as a main component. Examples of the crosslinking agent include compounds having any functional group of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and silane coupling agents. The anionic polymer and the crosslinking agent may be 1 species or 2 or more species, respectively.
In addition, the treatment liquid containing a chromium compound preferably contains an aminated phenol polymer from the viewpoint of exhibiting excellent corrosion resistance and improving the adhesion of the barrier layer having a corrosion-resistant coating film. The content of the aminated phenol polymer in the treatment liquid containing a chromium compound is preferably about 100 to 400 parts by mass, more preferably about 200 to 300 parts by mass, per 100 parts by mass of the chromium compound. The weight average molecular weight of the aminated phenol polymer is preferably about 5000 to 20000. The weight average molecular weight of the aminated phenol polymer is a value measured by Gel Permeation Chromatography (GPC) measured under the condition that polystyrene is used as a standard sample.
The solvent of the treatment liquid containing the chromium compound is not particularly limited as long as it can disperse the components contained in the treatment liquid and can be evaporated by heating thereafter, but water is preferably used.
The concentration of the solid content of the chromium compound contained in the treatment liquid for forming a corrosion-resistant coating is not particularly limited, and the peak intensity ratio P is determined byPO3/CrPO4The content of the above-mentioned predetermined range is, for example, about 1 to 15 mass%, preferably about 7.0 to 12.0 mass%, more preferably about 8.0 to 11.0 mass%, and still more preferably about 9.0 to 10.0 mass%, from the viewpoint of exhibiting excellent corrosion resistance and improving the adhesion of the barrier layer having a corrosion-resistant coating film.
The thickness of the corrosion-resistant coating is not particularly limited, and from the viewpoint of exhibiting excellent corrosion resistance and improving the adhesion of the barrier layer having the corrosion-resistant coating, the thickness is preferably about 1nm to 10 μm, more preferably about 1 to 100nm, and still more preferably about 1 to 50 nm. The thickness of the corrosion-resistant coating can be measured by observation with a transmission electron microscope or by a combination of observation with a transmission electron microscope and energy dispersive X-ray spectrometry or electron energy loss spectrometry.
From the same viewpoint, offAt each 1m2The amount of the corrosion-resistant coating film on the surface of the barrier layer 3 is preferably about 1 to 500mg, more preferably about 1 to 100mg, and still more preferably about 1 to 50 mg.
Examples of the method of applying the treatment liquid containing the chromium compound to the surface of the barrier layer include a bar coating method, a roll coating method, a gravure coating method, a dip coating method, and the like.
From the above peak intensity ratio PPO3/CrPO4In view of the above-mentioned predetermined range, from the viewpoint of exhibiting excellent corrosion resistance and improving the adhesion of the barrier layer having a corrosion-resistant coating, the heating temperature at the time of sintering the treatment liquid to form the corrosion-resistant coating is preferably about 170 to 250 ℃, more preferably about 180 to 230 ℃, and still more preferably about 190 to 220 ℃. From the same viewpoint, the sintering time is preferably about 2 to 10 seconds, and more preferably about 3 to 6 seconds.
From the viewpoint of more efficiently performing the chemical surface treatment of the surface of the barrier layer, it is preferable to perform the degreasing treatment by a known treatment method such as an alkali immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or an acid activation method before providing the corrosion-resistant coating film on the surface of the barrier layer 3.
[ Heat-fusible resin layer 4]
In the outer covering material for an electric storage device of the present invention, the heat-fusible resin layer 4 corresponds to the innermost layer, and is a layer (sealing layer) that functions to seal the electric storage device element by heat-fusing the heat-fusible resin layers to each other at the time of assembling the electric storage device.
The resin constituting the heat-weldable resin layer 4 is not particularly limited as long as it can be heat-welded, and is preferably a resin having a polyolefin skeleton, such as polyolefin and acid-modified polyolefin. Whether or not the resin constituting the heat-sealable resin layer 4 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, or the like. When the resin constituting the heat-fusible resin layer 4 is analyzed by infrared spectroscopy, it is preferable to detect a peak derived from maleic anhydride. For example, in the determination of maleic anhydride-modified polyolefin by infrared spectroscopyAt a wave number of 1760cm-1Neighborhood and wavenumber 1780cm-1A peak derived from maleic anhydride was detected in the vicinity. When the heat-sealable resin layer 4 is a layer made of maleic anhydride-modified polyolefin, a peak derived from maleic anhydride can be detected when measured by infrared spectroscopy. However, if the acid modification degree is low, the peak may become small and not detected. In this case, the analysis can be performed by nuclear magnetic resonance spectroscopy.
Specific examples of the polyolefin include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; ethylene-alpha olefin copolymers; polypropylene such as homopolypropylene, a block copolymer of polypropylene (for example, a block copolymer of propylene and ethylene), a random copolymer of polypropylene (for example, a random copolymer of propylene and ethylene), and the like; propylene-alpha olefin copolymers; ethylene-butene-propylene terpolymers, and the like. Among these, polypropylene is preferred. The polyolefin resin in the case of the copolymer may be a block copolymer or a random copolymer. These polyolefin-based resins may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Additionally, the polyolefin may be a cyclic polyolefin. The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin as a structural monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, isoprene, and the like. Examples of the cyclic monomer as a structural monomer of the cyclic polyolefin include cyclic olefins such as norbornene; cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene and norbornadiene. Among these, cyclic olefins are preferred, and norbornene is more preferred.
The acid-modified polyolefin refers to a polymer obtained by modifying a polyolefin by block polymerization or graft polymerization using an acid component. As the acid-modified polyolefin, the above-mentioned polyolefin, a copolymer obtained by copolymerizing polar molecules such as acrylic acid or methacrylic acid with the above-mentioned polyolefin, a polymer such as a crosslinked polyolefin, or the like can also be used. Examples of the acid component used for acid modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, and anhydrides thereof.
The acid-modified polyolefin may also be an acid-modified cyclic polyolefin. The acid-modified cyclic polyolefin may be a polymer obtained by copolymerizing a part of monomers constituting the cyclic polyolefin with an acid component, or by block polymerization or graft polymerization of the acid component to the cyclic polyolefin. The same applies to the cyclic polyolefin modified with an acid. The acid component used for the acid modification is the same as the acid component used for the modification of the polyolefin.
Examples of the preferred acid-modified polyolefin include polyolefins modified with a carboxylic acid or an anhydride thereof, polypropylene modified with a carboxylic acid or an anhydride thereof, maleic anhydride-modified polyolefins, and maleic anhydride-modified polypropylene.
The heat-fusible resin layer 4 may be formed of 1 resin alone or a blend polymer in which 2 or more resins are combined. Further, the heat-fusible resin layer 4 may be formed of only 1 layer, but may be formed of 2 or more layers of the same or different resins.
The heat-fusible resin layer 4 may contain a lubricant or the like as necessary. When the heat-fusible resin layer 4 contains a lubricant, the moldability of the outer covering material for an electricity storage device can be improved. The lubricant is not particularly limited, and a known lubricant can be used. The lubricant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The lubricant is not particularly limited, and preferably an amide-based lubricant is used. Specific examples of the lubricant include the lubricants exemplified for the first base material layer 11. The number of the lubricants may be 1 or more.
When the lubricant is present on the surface of the heat-fusible resin layer 4, the amount of the lubricant is not particularly limited, but is preferably 10 to 50mg/m from the viewpoint of improving the moldability of the outer covering material for an electricity storage device2About, more preferably 15 to 40mg/m2Left and right.
The lubricant present on the surface of the heat-fusible resin layer 4 may be a bleed-out lubricant contained in the resin constituting the heat-fusible resin layer 4, or may be a lubricant applied to the surface of the heat-fusible resin layer 4.
The thickness of the heat-fusible resin layer 4 is not particularly limited as long as the heat-fusible resin layers can perform a function of heat-fusing to seal the electric storage device element, and examples thereof include about 100 μm or less, preferably about 85 μm or less, and more preferably about 15 to 85 μm. For example, when the thickness of the adhesive layer 5 described later is 10 μm or more, the thickness of the heat-fusible resin layer 4 is preferably about 85 μm or less, and more preferably about 15 to 45 μm, and when the thickness of the adhesive layer 5 described later is less than 10 μm or when the adhesive layer 5 is not provided, the thickness of the heat-fusible resin layer 4 is preferably about 20 μm or more, and more preferably about 35 to 85 μm.
[ adhesive layer 5]
In the outer covering material for an electric storage device of the present invention, the adhesive layer 5 is a layer provided between the barrier layer 3 (or the corrosion-resistant film) and the heat-fusible resin layer 4 as needed to more firmly adhere them.
The adhesive layer 5 is formed of a resin capable of bonding the barrier layer 3 and the heat-fusible resin layer 4. As the resin for forming the adhesive layer 5, for example, the same resin as the adhesive exemplified in the first adhesive layer 21 can be used. The resin for forming the adhesive layer 5 preferably contains a polyolefin skeleton, and examples thereof include polyolefins and acid-modified polyolefins exemplified in the heat-sealable resin layer 4. Whether or not the resin constituting the adhesive layer 5 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, or the like, and the analysis method is not particularly limited. When the resin constituting the adhesive layer 5 is analyzed by infrared spectroscopy, it is preferable to detect a peak derived from maleic anhydride. For example, in the case of determining a maleic anhydride-modified polyolefin by infrared spectroscopy, the wave number is 1760cm-1Neighborhood and wavenumber 1780cm-1A peak derived from maleic anhydride was detected in the vicinity. However, if the degree of acid modification is low, the peak change occursSmall and not detected. In this case, the analysis can be performed by nuclear magnetic resonance spectroscopy.
The adhesive layer 5 preferably contains an acid-modified polyolefin from the viewpoint of firmly bonding the barrier layer 3 and the heat-fusible resin layer 4. As the acid-modified polyolefin, polyolefin modified with a carboxylic acid or an anhydride thereof, polypropylene modified with a carboxylic acid or an anhydride thereof, maleic anhydride-modified polyolefin, maleic anhydride-modified polypropylene are particularly preferable.
In addition, the adhesive layer 5 is more preferably a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, from the viewpoint of making the outer packaging material for an electrical storage device thin and having excellent shape stability after molding. The acid-modified polyolefin is preferably exemplified by those described above.
The adhesive layer 5 is preferably a cured product of a resin composition containing an acid-modified polyolefin and at least one selected from a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group, and is particularly preferably a cured product of a resin composition containing an acid-modified polyolefin and at least one selected from a compound having an isocyanate group and a compound having an epoxy group. The adhesive layer 5 preferably contains at least one selected from the group consisting of polyurethane, polyester, and epoxy resin, and more preferably contains polyurethane and epoxy resin. As the polyester, for example, an amide ester resin is preferable. Amide ester resins are generally formed by the reaction of a carboxyl group with an oxazoline group. The adhesive layer 5 is more preferably a cured product of a resin composition containing at least one of these resins and the acid-modified polyolefin. When an unreacted material of a curing agent such as a compound having an isocyanate group, a compound having an oxazoline group, or an epoxy resin remains in the adhesive layer 5, the presence of the unreacted material can be confirmed by a method selected from infrared spectroscopy, raman spectroscopy, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the like.
From the viewpoint of further improving the adhesion between the barrier layer 3 and the adhesive layer 5, the adhesive layer 5 is preferably a cured product of a resin composition containing a curing agent having at least one selected from an oxygen atom, a heterocycle, a C ═ N bond, and a C — O — C bond. Examples of the curing agent having a heterocyclic ring include a curing agent having an oxazoline group, a curing agent having an epoxy group, and the like. Examples of the curing agent having a C ═ N bond include a curing agent having an oxazoline group and a curing agent having an isocyanate group. Examples of the curing agent having a C — O — C bond include a curing agent having an oxazoline group, a curing agent having an epoxy group, and polyurethane. The cured product of the resin composition having the adhesive layer 5 containing the curing agent can be confirmed by, for example, Gas Chromatography Mass Spectrometry (GCMS), infrared spectroscopy (IR), time of flight secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectroscopy (XPS), and the like.
The compound having an isocyanate group is not particularly limited, but a polyfunctional isocyanate compound is preferably used from the viewpoint of effectively improving the adhesion between the barrier layer 3 and the adhesive layer 5. The polyfunctional isocyanate compound is not particularly limited as long as it has 2 or more isocyanate groups. Specific examples of the polyfunctional isocyanate-based curing agent include Pentane Diisocyanate (PDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), Tolylene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), a polymer or a urethanized product thereof, a mixture thereof, and a copolymer with another polymer. Further, an adduct, a biuret, an isocyanurate, and the like can be cited.
The content of the compound having an isocyanate group in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and more preferably in the range of 0.5 to 40% by mass, in the resin composition constituting the adhesive layer 5. This can effectively improve the adhesion between the barrier layer 3 and the adhesive layer 5.
The oxazoline group-containing compound is not particularly limited as long as it is a compound having an oxazoline skeleton. Specific examples of the oxazoline group-containing compound include a compound having a polystyrene main chain, a compound having an acrylic main chain, and the like. Examples of commercially available products include EPOCROS series products manufactured by japan catalyst corporation.
The proportion of the oxazoline group-containing compound in the adhesive layer 5 is preferably in the range of 0.1 to 50 mass%, more preferably 0.5 to 40 mass% in the resin composition constituting the adhesive layer 5. This can effectively improve the adhesion between the barrier layer 3 and the adhesive layer 5.
Examples of the compound having an epoxy group include epoxy resins. The epoxy resin is not particularly limited as long as it is a resin capable of forming a crosslinked structure by utilizing epoxy groups present in the molecule, and a known epoxy resin can be used. The weight average molecular weight of the epoxy resin is preferably about 50 to 2000, more preferably about 100 to 1000, and still more preferably about 200 to 800. In the first invention, the weight average molecular weight of the epoxy resin is a value measured by Gel Permeation Chromatography (GPC) measured under the condition that polystyrene is used as a standard sample.
Specific examples of the epoxy resin include glycidyl ether derivatives of trimethylolpropane, bisphenol a diglycidyl ether, modified bisphenol a diglycidyl ether, novolac glycidyl ether, glycerol polyglycidyl ether, and polyglycerol polyglycidyl ether. The epoxy resin may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The proportion of the epoxy resin in the adhesive layer 5 is preferably in the range of 0.1 to 50 mass%, more preferably 0.5 to 40 mass% in the resin composition constituting the adhesive layer 5. This can effectively improve the adhesion between the barrier layer 3 and the adhesive layer 5.
The polyurethane is not particularly limited, and known polyurethane can be used. The adhesive layer 5 may be a cured product of 2-liquid curable polyurethane, for example.
The proportion of the polyurethane in the adhesive layer 5 is preferably in the range of 0.1 to 50 mass%, more preferably 0.5 to 40 mass% in the resin composition constituting the adhesive layer 5. This can effectively improve the adhesion between the barrier layer 3 and the adhesive layer 5 in an atmosphere containing a component such as an electrolyte solution that induces corrosion of the barrier layer.
In the case where the adhesive layer 5 is a cured product of a resin composition containing at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group and an epoxy resin, and the acid-modified polyolefin, the acid-modified polyolefin functions as a main agent, and the compound having an isocyanate group, the compound having an oxazoline group and the compound having an epoxy group function as curing agents, respectively.
The upper limit of the thickness of the adhesive layer 5 is preferably about 50 μm or less, about 40 μm or less, about 30 μm or less, about 20 μm or less, and about 5 μm or less, the lower limit is preferably about 0.1 μm or more and about 0.5 μm or more, and the ranges of the thickness are preferably about 0.1 to 50 μm, about 0.1 to 40 μm, about 0.1 to 30 μm, about 0.1 to 20 μm, about 0.1 to 5 μm, about 0.5 to 50 μm, about 0.5 to 40 μm, about 0.5 to 30 μm, about 0.5 to 20 μm, and about 0.5 to 5 μm. More specifically, the adhesive exemplified for the adhesive layer 2 or the cured product of the acid-modified polyolefin and the curing agent is preferably about 1 to 10 μm, and more preferably about 1 to 5 μm. When the resin exemplified in the heat-fusible resin layer 4 is used, it is preferably about 2 to 50 μm, and more preferably about 10 to 40 μm. When the adhesive layer 5 is the adhesive exemplified in the adhesive layer 2 or a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 5 can be formed by, for example, applying the resin composition and then curing the resin composition by heating or the like. In the case of using the resin exemplified for the heat-fusible resin layer 4, the resin can be formed by, for example, extrusion molding the heat-fusible resin layer 4 and the adhesive layer 5.
[ surface coating layer 6]
The outer packaging material for an electric storage device of the present invention may have a surface coating layer 6 on the first substrate layer 11 (on the side opposite to the barrier layer 3 of the first substrate layer 11) as necessary for the purpose of improving at least one of design properties, electrolyte resistance, scratch resistance, moldability, and the like. The surface coating layer 6 is a layer located on the outermost layer side of the outer packaging material for an electric storage device when the electric storage device is assembled using the outer packaging material for an electric storage device.
The surface covering layer 6 can be formed of a resin such as polyvinylidene chloride, polyester, polyurethane, acrylic resin, epoxy resin, or the like.
When the resin forming the surface-covering layer 6 is a curable resin, the resin may be any of a 1-liquid curable resin and a 2-liquid curable resin, and a 2-liquid curable resin is preferable. Examples of the 2-liquid curable resin include 2-liquid curable polyurethane, 2-liquid curable polyester, and 2-liquid curable epoxy resin. Among these, 2-liquid curable polyurethane is preferable.
The 2-liquid curable polyurethane includes, for example, a polyurethane containing a main agent containing a polyol compound and a curing agent containing an isocyanate compound. Preferably, the polyurethane is a two-pack curable polyurethane comprising a polyol such as a polyester polyol, a polyether polyol or an acrylic polyol as a main component and an aromatic or aliphatic polyisocyanate as a curing agent. In addition, as the polyol compound, a polyester polyol having a hydroxyl group in a side chain in addition to a hydroxyl group at the terminal of the repeating unit is preferably used. By forming the surface-covering layer 6 of polyurethane, excellent electrolyte resistance can be imparted to the outer covering material for an electric storage device.
The surface-covering layer 6 may contain additives such as the above-mentioned lubricant, antiblocking agent, matting agent, flame retardant, antioxidant, thickener, antistatic agent, and the like, as necessary, on at least one of the surface and the inside of the surface-covering layer 6, in accordance with the functionality and the like to be provided to the surface-covering layer 6 or the surface thereof. Examples of the additive include fine particles having an average particle diameter of about 0.5nm to 5 μm. The average particle diameter of the additive is the median diameter measured by a laser diffraction/scattering particle size distribution measuring apparatus.
The additive may be any of inorganic and organic. The shape of the additive is not particularly limited, and examples thereof include spherical, fibrous, plate-like, amorphous, and scaly shapes.
Specific examples of the additive include talc, silica, graphite, kaolin, montmorillonite, mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, aluminum oxide, carbon black, carbon nanotubes, high-melting nylon, acrylate resins, crosslinked acrylic acid, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, and nickel. The additive may be used alone in 1 kind, or 2 or more kinds may be used in combination. Among these additives, silica, barium sulfate, and titanium oxide are preferable from the viewpoints of dispersion stability, cost, and the like. The surface of the additive may be subjected to various surface treatments such as an insulating treatment and a high-dispersibility treatment.
The method for forming the surface-covering layer 6 is not particularly limited, and for example, a method of applying a resin for forming the surface-covering layer 6 is mentioned. When the surface-covering layer 6 contains an additive, a resin mixed with the additive may be applied.
The thickness of the surface-covering layer 6 is not particularly limited as long as the surface-covering layer 6 can exhibit the above-described functions, and examples thereof include about 0.5 to 10 μm, preferably about 1 to 5 μm.
3. Method for producing outer packaging material for electricity storage device
The method for producing the outer packaging material for an electricity storage device is not particularly limited as long as the layers included in the outer packaging material for an electricity storage device of the present invention can be laminated to obtain a laminate, and a method including a step of sequentially laminating at least the first base material layer 11, the first adhesive layer 21, the second base material layer 12, the second adhesive layer 22, the barrier layer 3, and the heat-fusible resin layer 4 is exemplified. That is, the method for producing an outer packaging material for an electricity storage device of the present invention includes a step of laminating at least a first base material layer, a first adhesive layer, a second base material layer, a second adhesive layer, a barrier layer, and a heat-fusible resin layer in this order to obtain a laminate, and the barrier layer is laminated on the laminateWhen the corrosion-resistant coating is analyzed by time-of-flight secondary ion mass spectrometry, the corrosion-resistant coating is derived from PO3 -Peak intensity P ofPO3Relative to that derived from CrPO4 -Peak intensity P ofCrPO4Ratio PPO3/CrPO4In the range of 6 to 120.
An example of the method for producing the outer packaging material for an electric storage device of the present invention is as follows. First, a laminate (hereinafter, also referred to as "laminate a") in which the first base material layer 11, the first adhesive layer 21, the second base material layer 12, the second adhesive layer 22, and the barrier layer 3 are laminated in this order is formed. In forming the laminate a, it is preferable to prepare a laminate in which the first base material layer 11, the first adhesive layer 21, and the second base material layer 12 are laminated in this order. The laminate can be produced by a dry lamination method in which an adhesive for forming the first adhesive layer 21 is applied to the first base material layer 11 or the second base material layer 12 by a coating method such as a gravure coating method or a roll coating method, dried, and then the first base material layer 11 and the second base material layer 12 are laminated with the adhesive interposed therebetween, and then the first adhesive layer 21 is cured. Then, an adhesive for forming the second adhesive layer 22 is applied and dried by a coating method such as a gravure coating method or a roll coating method on the second base material layer 12 side or the barrier layer 3 (having a corrosion-resistant coating film) of the obtained laminate, and then the second base material layer 12 side of the laminate and the barrier layer 3 are laminated via the adhesive, and then the second adhesive layer 22 is cured, thereby obtaining a laminate a by a dry lamination method.
Next, the adhesive layer 5 and the heat-fusible resin layer 4 are sequentially laminated on the barrier layer 3 of the laminate a. For example, there can be mentioned (1) a method of laminating the adhesive layer 5 and the heat-fusible resin layer 4 on the barrier layer 3 of the laminate a by coextrusion (coextrusion lamination method); (2) a method of forming a laminate in which the adhesive layer 5 and the heat-fusible resin layer 4 are laminated, and laminating the laminate on the barrier layer 3 of the laminate A by a heat lamination method; (3) a method in which an adhesive for forming an adhesive layer 5 is laminated on the barrier layer 3 of the laminate a by an extrusion method, a method in which the adhesive is applied with a solution, dried at a high temperature, and then sintered, and a heat-fusible resin layer 4 previously formed in a sheet shape is laminated on the adhesive layer 5 by a heat lamination method; (4) a method (sandwich lamination method) in which the laminate a and the heat-fusible resin layer 4 are bonded to each other through the adhesive layer 5 while the molten adhesive layer 5 is poured between the barrier layer 3 of the laminate a and the heat-fusible resin layer 4 formed in a sheet shape in advance.
When the surface-covering layer 6 is provided, the surface-covering layer 6 is laminated on the surface of the first base material layer 11 opposite to the barrier layer 3. The surface-covering layer 6 can be formed by, for example, applying the resin forming the surface-covering layer 6 to the surface of the first base material layer 11. The order of the step of laminating the barrier layer 3 on the surface of the first base material layer 11 and the step of laminating the surface-covering layer 6 on the surface of the first base material layer 11 is not particularly limited. For example, after the surface-covering layer 6 is formed on the surface of the first base material layer 11, the barrier layer 3 may be formed on the surface of the first base material layer 11 opposite to the surface-covering layer 6.
The curing of the first adhesive layer 21 can be performed, for example, by curing at the stage of obtaining a laminate of the first base material layer 11, the first adhesive layer 21, and the second base material layer 12, or by curing a laminate a in which the barrier layer 3 is laminated. The curing of the second adhesive layer 22 can be performed by curing a laminate of the second base material layer 12, the second adhesive layer 22 and the barrier layer, or by curing the laminate a, or by laminating an adhesive layer 5, a heat-fusible resin layer 4 and the like provided as needed, and then curing the laminate. The curing conditions of the first adhesive layer 21 and the second adhesive layer 22 are adjusted to achieve the predetermined hardness, as described above, depending on the type of adhesive used to form these layers, and the like. The conditions for the aging are not particularly limited, and for example, the temperature is about 60 to 120 ℃ and the time is about 12 to 120 hours.
As described above, a laminate comprising the surface covering layer 6, the first base material layer 11, the first adhesive layer 21, the second base material layer 12, the second adhesive layer 22, the barrier layer 3 having a corrosion-resistant coating film on at least one surface thereof, the adhesive layer 5, and the heat-sealable resin layer 4 may be formed, and heat treatment such as heat roller contact treatment, hot air treatment, near infrared ray treatment, far infrared ray treatment, or the like may be applied to the laminate in order to enhance the adhesiveness of the first adhesive layer 21 or the second adhesive layer 22. The conditions for such heat treatment include, for example, 1 to 5 minutes at 150 to 250 ℃.
In the outer covering material for an electric storage device, each layer constituting the laminate may be subjected to surface activation treatment such as corona treatment, blast treatment, oxidation treatment, or ozone treatment as necessary to improve the processing suitability. For example, by performing corona treatment on the surface of the first base material layer 11 opposite to the barrier layer 3, the printability of the ink on the surface of the first base material layer 11 can be improved.
4. Use of outer packaging material for electricity storage device
The outer package for an electric storage device of the present invention is used for a package for sealing and housing electric storage device elements such as a positive electrode, a negative electrode, and an electrolyte. That is, the electric storage device element including at least the positive electrode, the negative electrode, and the electrolyte is housed in the package formed of the outer packaging material for an electric storage device of the present invention, and the electric storage device can be manufactured.
Specifically, an electric storage device element including at least a positive electrode, a negative electrode, and an electrolyte is covered with the outer covering material for an electric storage device of the present invention so that a flange portion (a region where heat-fusible resin layers are in contact with each other) can be formed at an edge of the electric storage device element in a state where a metal terminal connected to each of the positive electrode and the negative electrode protrudes to the outside, and the heat-fusible resin layers of the flange portion are heat-sealed with each other, whereby an electric storage device using the outer covering material for an electric storage device can be provided. When the electric storage device element is housed in the package formed of the electric storage device exterior material of the present invention, the package is formed so that the heat-fusible resin portion of the electric storage device exterior material of the present invention is on the inside (the surface that contacts the electric storage device element).
The outer package for an electric storage device of the present invention can be preferably used for an electric storage device such as an electric storage device (including a capacitor, and the like). The outer packaging material for power storage devices of the present invention can be used for either primary power storage devices or secondary power storage devices, and is preferably a secondary power storage device. The type of secondary electricity storage device to which the outer covering material for an electricity storage device of the present invention can be applied is not particularly limited, and examples thereof include a lithium ion electricity storage device, a lithium ion polymer electricity storage device, an all-solid electricity storage device, a lead storage battery, a nickel-hydrogen storage battery, a nickel-cadmium storage battery, a nickel-iron storage battery, a nickel-zinc storage battery, a silver oxide-zinc storage battery, a metal air electricity storage device, a polyvalent cation electricity storage device, a capacitor (condenser), a capacitor (capacitor), and the like. Among these secondary power storage devices, lithium ion power storage devices and lithium ion polymer power storage devices are preferable as an application target of the outer cover for power storage devices of the present invention.
Examples
The present invention will be described in detail below with reference to examples and comparative examples. However, the present invention is not limited to the examples.
< production of exterior Material for electric storage device >
Example 1
A laminate comprising a first base material layer/a first adhesive layer/a second base material layer laminated in this order was obtained by applying a 2-liquid urethane adhesive (a polyol compound and an aromatic isocyanate compound, the cured thickness being 3 μm) for forming a first adhesive layer on a first base material layer comprising a stretched nylon film (thickness 15 μm) by a dry lamination method, and laminating a second base material layer comprising a stretched nylon film (thickness 25 μm) thereon. Then, both surfaces of the obtained laminate on the second base material layer side were subjected to chemical surface treatment by the method described later, and a barrier layer comprising an aluminum alloy foil (JIS H4160: 1994A8021H-O, thickness 40 μm) having a corrosion-resistant coating (thickness 10nm) was laminated by a dry lamination method. Specifically, a 2-pack type urethane adhesive (a polyol compound and an aromatic isocyanate compound) for forming a second adhesive layer was applied to one surface of an aluminum alloy foil having a corrosion-resistant coating, and the second adhesive layer (having a thickness of 3 μm after curing) was formed on the barrier layer. Then, the second adhesive layer on the barrier layer was laminated on the second base layer side of the laminate to prepare a laminate a of the first base layer/first adhesive layer/second base layer/second adhesive layer/barrier layer.
The laminate a was subjected to curing treatment under the curing treatment conditions shown in table 1, and the hardness of the first adhesive layer and the second adhesive layer was adjusted. Specifically, the laminate a having the first base material layer/first adhesive layer/second base material layer/second adhesive layer/barrier layer laminated in this order was cured under the curing conditions of example 1 under the curing conditions shown in table 1 (at 80 ℃ for 24 hours).
The formation of the corrosion-resistant coating on the surface of the barrier layer is performed as follows. A treatment solution containing 43 parts by mass of an aminated phenol polymer, 16 parts by mass of chromium fluoride and 13 parts by mass of phosphoric acid per 100 parts by mass was prepared, the treatment solution was applied to both surfaces of a barrier layer (the film thickness after drying was 10nm), and the barrier layer was dried by heating at a temperature of about 190 to 230 ℃ for about 3 to 6 seconds.
Then, maleic anhydride-modified polypropylene (thickness 20 μm) as an adhesive layer and random polypropylene (thickness 15 μm) as a heat-fusible resin layer were coextruded on the barrier layer of the obtained laminate a, and the adhesive layer/heat-fusible resin layer was laminated on the barrier layer to obtain an outer casing for an electricity storage device comprising a laminate B in which a first base material layer (15 μm)/a first adhesive layer (3 μm)/a second base material layer (25 μm)/a second adhesive layer (3 μm)/a barrier layer (40 μm)/an adhesive layer (20 μm)/a heat-fusible resin layer (15 μm) were laminated in this order.
Example 2
An exterior material for a power storage device comprising a laminate B in which a first base material layer (15 μm)/a first adhesive layer (3 μm)/a second base material layer (25 μm)/a second adhesive layer (3 μm)/a barrier layer (35 μm)/an adhesive layer (20 μm)/a heat-sealable resin layer (15 μm) were laminated in this order was obtained in the same manner as in example 1, except that an aluminum alloy foil (JIS H4160: 1994A8021H-O, thickness 35 μm) having the same corrosion-resistant coating film (thickness 10nm) as in example 1 was used as the barrier layer.
Example 3
An exterior material for an electricity storage device, which included a laminate B in which a first base material layer (15 μm)/a first adhesive layer (3 μm)/a second base material layer (15 μm)/a second adhesive layer (3 μm)/a barrier layer (40 μm)/an adhesive layer (23 μm)/a heat-fusible resin layer (22 μm) were sequentially laminated, was obtained in the same manner as in example 1, except that a stretched nylon film (15 μm in thickness) was used as the second base material layer, and maleic anhydride-modified polypropylene (23 μm) as the adhesive layer and random polypropylene (22 μm in thickness) as the heat-fusible resin layer were coextruded to laminate the adhesive layer/the heat-fusible resin layer on the barrier layer.
Example 4
A stretched nylon film (thickness: 15 μm) was used as the second base material layer, a maleic anhydride-modified polypropylene (thickness: 40 μm) as an adhesive layer and a random polypropylene (thickness: 40 μm) as a heat-fusible resin layer were coextruded to laminate the adhesive layer/heat-fusible resin layer on the barrier layer, and the first base material layer/first adhesive layer/second base material layer/second adhesive layer/barrier layer were simultaneously cured under the curing conditions (at 120 ℃ C. and 24 hours) shown in Table 1 to obtain a laminate A comprising the first base material layer (15 μm)/first adhesive layer (3 μm)/second base material layer (15 μm)/second adhesive layer (3 μm)/second adhesive layer (40 μm)/adhesive layer (40 μm) laminated in this order in the same manner as in example 1 Laminate B of heat-fusible resin layer (40 μm) as an outer covering material for an electric storage device.
Example 5
A second base material layer comprising a stretched nylon film (thickness 15 μm) was laminated on a barrier layer comprising an aluminum alloy foil (JIS H4160: 1994A8021H-O, thickness 40 μm) having the same corrosion-resistant coating as in example 1 by dry lamination. Specifically, a 2-pack type urethane adhesive (a polyol compound and an aromatic isocyanate compound) for forming a second adhesive layer was applied to one surface of an aluminum alloy foil having a corrosion-resistant coating film, the second adhesive layer (having a thickness of 3 μm after curing) was formed on a barrier layer, and a second base layer comprising stretched nylon was laminated thereon to obtain a laminate of the second base layer/the second adhesive layer/the barrier layer. Then, a 2-liquid urethane adhesive (a polyol compound and an aromatic isocyanate compound, and having a cured thickness of 3 μm) for forming a first adhesive layer was applied to the second base layer side of the laminate by a dry lamination method, and a first base layer including a 2-axis stretched polyethylene terephthalate film (having a thickness of 15 μm) was laminated thereon to prepare a laminate a of a first base layer/a first adhesive layer/a second base layer/a second adhesive layer/a barrier layer.
The curing treatment was performed under the curing treatment conditions shown in table 1, and the hardness of the first adhesive layer and the second adhesive layer was adjusted. Specifically, in the curing treatment conditions of example 5, the curing of the second adhesive layer was performed under the curing treatment conditions (at 80 ℃ for 24 hours) shown in table 1 in the step of producing the laminate of the second base layer/the second adhesive layer/the barrier layer, and then the curing of the first adhesive layer was performed under the curing treatment conditions (at 60 ℃ for 24 hours) shown in table 1 in the step of producing the laminate a in which the first base layer/the first adhesive layer/the second base layer/the second adhesive layer/the barrier layer were sequentially laminated.
The formation of the corrosion-resistant coating on the surface of the barrier layer was performed in the same manner as in example 1.
Then, maleic anhydride-modified polypropylene (thickness 40 μm) as an adhesive layer and random polypropylene (thickness 40 μm) as a heat-fusible resin layer were coextruded on the barrier layer of the obtained laminate a, and the adhesive layer/heat-fusible resin layer was laminated on the barrier layer to obtain an outer casing for an electricity storage device comprising a laminate B in which a first base material layer (15 μm)/a first adhesive layer (3 μm)/a second base material layer (15 μm)/a second adhesive layer (3 μm)/a barrier layer (40 μm)/an adhesive layer (40 μm)/a heat-fusible resin layer (40 μm) were laminated in this order.
Example 6
A stretched nylon film (thickness: 15 μm) was used as the second base material layer, a maleic anhydride-modified polypropylene (thickness: 40 μm) as an adhesive layer and a random polypropylene (thickness: 40 μm) as a heat-fusible resin layer were coextruded to laminate the adhesive layer/heat-fusible resin layer on the barrier layer, and the first base material layer/first adhesive layer/second base material layer/second adhesive layer/barrier layer were simultaneously cured under the curing conditions (at 40 ℃ C., 24 hours) shown in Table 1 for the laminate A having the first base material layer/first adhesive layer/second base material layer/second adhesive layer/barrier layer laminated in this order, to obtain a laminate comprising the first base material layer (15 μm)/first adhesive layer (3 μm)/second base material layer (15 μm)/second adhesive layer (3 μm)/second adhesive layer (40 μm)/adhesive layer (40 μm) Laminate B of heat-fusible resin layer (40 μm) as an outer covering material for an electric storage device.
Example 7
The laminate a having the first base material layer/first adhesive layer/second base material layer/second adhesive layer/barrier layer laminated in this order was cured under the curing conditions (at 120 ℃ for 24 hours) shown in table 1 at the stage of producing the laminate of the second base material layer/second adhesive layer/barrier layer, and then cured under the curing conditions (at 40 ℃ for 24 hours) shown in table 1 at the stage of producing the laminate a having the first base material layer/first adhesive layer/second base material layer/second adhesive layer/barrier layer laminated in this order, except that the laminate a having the first base material layer/first adhesive layer/second base material layer/second adhesive layer/barrier layer laminated in this order was obtained in the same manner as in example 5, and the laminate a having the first base material layer (15 μm)/first adhesive layer (3 μm)/second base material layer (15 μm)/second adhesive layer (3 μm)/barrier layer (40 μm) laminated in this order was obtained ) Laminate B consisting of adhesive layer (40 μm)/heat-fusible resin layer (40 μm).
Example 8
A2-axis stretched polyethylene terephthalate film (thickness: 12 μm) was used as the first base material layer, a stretched nylon film (thickness: 15 μm) was used as the second base material layer, maleic anhydride-modified polypropylene (thickness: 40 μm) as the adhesive layer and atactic polypropylene (thickness: 40 μm) as the heat-sealable resin layer were coextruded, in the same manner as in example 1 except that the adhesive layer/heat-fusible resin layer was laminated on the barrier layer, an outer casing for an electricity storage device comprising a laminate B in which a first base material layer (12 μm)/a first adhesive layer (3 μm)/a second base material layer (15 μm)/a second adhesive layer (3 μm)/a barrier layer (40 μm)/an adhesive layer (40 μm)/a heat-fusible resin layer (40 μm) were laminated in this order was obtained.
Example 9
A stretched nylon film (thickness: 15 μm) was used as the second base material layer, and maleic anhydride-modified polypropylene (thickness: 23 μm) as an adhesive layer and atactic polypropylene (thickness: 22 μm) as a heat-sealable resin layer were coextruded to laminate an adhesive layer/heat-sealable resin layer on the barrier layer, an exterior material for an electric storage device including a laminate B in which a first base material layer (15 μm)/a first adhesive layer (3 μm)/a second base material layer (15 μm)/a second adhesive layer (3 μm)/a barrier layer (40 μm)/an adhesive layer (23 μm)/a heat-fusible resin layer (22 μm) were sequentially laminated was obtained in the same manner as in example 1 except that the content of phosphoric acid was changed to about 1/2 times (mass ratio) that in example 1 when forming the corrosion-resistant coating film on the surface of the barrier layer.
Example 10
A stretched nylon film (thickness: 15 μm) was used as the second base material layer, and maleic anhydride-modified polypropylene (thickness: 23 μm) as an adhesive layer and atactic polypropylene (thickness: 22 μm) as a heat-fusible resin layer were coextruded to laminate an adhesive layer/heat-fusible resin layer on the barrier layer, an exterior material for an electric storage device including a laminate B in which a first base material layer (15 μm)/a first adhesive layer (3 μm)/a second base material layer (15 μm)/a second adhesive layer (3 μm)/a barrier layer (40 μm)/an adhesive layer (23 μm)/a heat-fusible resin layer (22 μm) were sequentially laminated was obtained in the same manner as in example 1 except that the content of phosphoric acid was changed to about 1.3 times (mass ratio) the content of the corrosion-resistant coating film on the surface of the barrier layer in example 1.
Comparative examples 1 and 2
A barrier layer comprising an aluminum alloy foil (JIS H4160: 1994A8021H-O, thickness 40 μm) having a corrosion-resistant coating film (thickness 10nm) was laminated by a dry lamination method by chemically treating both surfaces of a 2-axis drawn nylon film (25 μm) as a base material layer by the method described later. Specifically, a 2-pack type urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of an aluminum alloy foil having a corrosion-resistant coating film to form an adhesive layer (thickness: 3 μm). Then, the adhesive layer on the barrier layer having the corrosion-resistant film and the 2-axis stretched nylon film side of the base material layer were laminated, and then subjected to aging treatment (after standing at 60 ℃ for 24 hours, and further standing at 80 ℃ for 24 hours), to prepare a laminate of 2-axis stretched nylon film/adhesive layer/barrier layer having corrosion-resistant films on both surfaces.
Then, maleic anhydride-modified polypropylene (23 μm) as an adhesive layer and random polypropylene (23 μm) as a heat-fusible resin layer were laminated on the barrier layer of the laminate by co-extrusion of maleic anhydride-modified polypropylene and random polypropylene. Then, the obtained laminate was cured to obtain an outer covering material for electricity storage devices, in which a 2-axis stretched nylon film (25 μm)/adhesive layer (3 μm)/barrier layer (40 μm)/maleic anhydride-modified polypropylene (23 μm)/random polypropylene (23 μm) having corrosion-resistant films (10nm) on both surfaces were sequentially laminated.
A corrosion-resistant coating was formed in the same manner as in example 1 except that in comparative example 1, phosphoric acid was used at about 1/3 times (mass ratio) as in example 1, and in comparative example 2, phosphoric acid was used at about 1.5 times (mass ratio) as in example, and chemical surface treatment was performed, when forming a corrosion-resistant coating on the surface of the barrier layer.
< time-of-flight type secondary ion mass spectrometry >
The corrosion-resistant coating was analyzed as follows. First, the barrier layer and the adhesive layer are peeled off. In this case, physical peeling is employed without using water, an organic solvent, an aqueous solution of an acid or an alkali, or the like. Bonding the barrier layer to the adhesiveAfter the bonding layers are peeled off from each other, the adhesive layer remains on the surface of the barrier layer, and thus the remaining adhesive layer is removed by Ar-GCIB etching. The surface of the barrier layer thus obtained was analyzed for a corrosion-resistant coating by time-of-flight secondary ion mass spectrometry. Respectively derived from CrPO4 -And PO3 -Peak intensity P ofCrPO4And PPO3And peak intensity PPO3Relative to peak intensity PCrPO4Ratio PPO3/CrPO4Are shown in Table 1, respectively.
The details of the measuring apparatus and the measuring conditions of the time-of-flight secondary ion mass spectrometry are as follows.
A measuring device: SIMS5, time-of-flight secondary ION mass spectrometer manufactured by ION-TOF
(measurement conditions)
Primary ion: bi-charged ions (Bi) of bismuth clusters3 ++)
Primary ion acceleration voltage: 30kV
Mass range (m/z): 0 to 1500
Measurement range: 100 μm × 100 μm
Scanning number: 16 scans/cycles (scan/cycle)
Number of pixels (1 side): 256pixel
Etching ions: ar gas cluster ion beam (Ar-GCIB)
Etching ion acceleration voltage: 5.0kV
< evaluation of adhesion >
The adhesion between the barrier layer and the heat-fusible resin layer when the electrolyte was adhered to the exterior material for an electricity storage device was evaluated by measuring the peel strength (N/15mm) by the following method.
First, each of the outer packaging materials for electric storage devices obtained above was cut into a size of 15mm (TD: Transverse Direction) and 100mm (MD: Machine Direction) to prepare a test piece. A test piece was placed in a glass bottle, and an electrolyte solution (obtained by mixing ethylene carbonate, diethyl carbonate, and dimethyl carbonate at a volume ratio of 1: 1: 1) was addedThe solution contained lithium hexafluorophosphate (concentration in solution 1X 10)3mol/m3) So that the electrolyte soaks the entire test piece. In this state, the glass bottle was capped and sealed. The sealed glass bottle was placed in an oven set at 85 ℃ and allowed to stand for 24 hours. After that, the glass bottle was taken out of the oven, and the test piece was taken out of the glass bottle and washed with water, and then the surface of the test piece was wiped off with a towel.
Thereafter, the test piece was peeled off from the barrier layer, and the test piece was stretched in a direction of 180 ° at a standard interline distance of 50mm and a speed of 50 mm/min using a tensile tester (trade name AG-XPlus manufactured by shimadzu corporation) to measure the peel strength (N/15mm) of the test piece. The peel strength of the test piece was measured within 10 minutes after the moisture on the surface of the test piece was wiped off with a towel. The strength at a distance of 57mm between the reticles was defined as the peel strength of the test piece.
On the other hand, the initial adhesion was evaluated in the following manner. First, each of the outer packaging materials for electricity storage devices obtained above was cut into a size of 15mm (td) and 100mm (md), respectively, to obtain test pieces. Thereafter, the test piece was peeled off from the barrier layer, and the heat-fusible resin layer and the barrier layer were stretched in a direction of 180 ℃ at a speed of 50 mm/min from the gauge line by using a tensile tester (trade name AG-XPlus manufactured by Shimadzu corporation), and the peel strength (N/15mm) of the test piece was measured. The results are shown in Table 1. The peel strength in the initial adhesion was defined as 100%, and the rate of maintenance of the peel strength and the peel strength (after 24 hours) in the adhesion after immersion in the electrolyte solution are also shown in table 1. When the heat-fusible resin layer and the barrier layer are peeled off from each other, the adhesive layer located between these layers is laminated on either one or both of the heat-fusible resin layer and the barrier layer.
< measurement of hardness of respective layers >
As the apparatus, a nanoindenter ("TriboInder TI 950" manufactured by Haesi corporation) was usedIndenter for nanoindenter, the Berkovich indenter (triangular pyramid) was used. First, in an environment with a relative humidity of 50% and 23 ℃, the indenter was pressed against the surface of the second adhesive layer (the surface of the second adhesive layer exposed, the direction perpendicular to the lamination direction of the layers) of the outer packaging material for an electric storage device, taking 10 seconds, and the indenter was pressed into the adhesive layer from the surface until the load reached 40 μ N, and held in this state for 5 seconds, and then, the load was removed taking 10 seconds. Using maximum load Pmax(μ N) projected area of contact A (μm) at maximum depth2) From PmaxThe indentation hardness (MPa) was calculated. The mean value was taken at assay 5 with change in assay site. The hardness of the first adhesive layer was measured in the same manner as the second adhesive layer, except that the load was set to 10 μ N. The respective hardness is shown in table 1. The surface of the press-fit indenter is a portion obtained by cutting in the thickness direction so as to pass through the center portion of the outer covering material for an electric storage device, and a cross section of the measurement object (such as the second adhesive layer) is exposed. The cutting is performed using a commercially available rotary Microtome (Microtome) or the like. In comparative examples 1 and 2, the base material layer was 1 layer, and no layer corresponding to the first adhesive layer was present, so that the measurement of the hardness of the adhesive layer was omitted, and the results are shown as "-" in table 1.
< evaluation of moldability >
Each of the outer packaging materials for electric storage devices obtained above was cut into a rectangular shape having a length (direction of md (machine direction)) of 90mm × width (direction of td (transverse direction)) of 150mm, and the rectangular shape was used as a test sample. For this sample, 10 samples were cold-formed (vacuum 1-time forming) by changing the forming depth in 0.5mm units from the forming depth of 0.5mm using a rectangular forming die (female die, JIS B0659-1: 2002 annex 1 (reference) for its surface) having a caliber of 31.6Mm (MD) × 54.5mm (TD direction) and a maximum height roughness (nominal value of Rz) specified in table 2 for the comparative surface roughness standard sheet of 3.2 μm, corner r2.0mm, ridge r1.0mm) and a forming die corresponding thereto (male die, JIS B0659-1: 2002 1 (reference) for its surface) and a maximum height roughness (nominal value of Rz) specified in table 2 for the comparative surface roughness standard sheet of 1.6 μm, corner r2.0mm, ridge r1.0mm) with a pressing pressure (surface pressure) of 0.25 MPa. At this time, the test specimen was placed on a female mold and molded so that the heat-fusible resin layer side was positioned on the male mold side. Further, the clearance between the male mold and the female mold was 0.3 mm. For the cold-formed sample, light was irradiated with a pen-shaped torch in a dark room, and whether or not pinholes and cracks were generated in the aluminum alloy foil was confirmed by whether or not light was transmitted. The deepest molding depth at which no pinholes or cracks were formed in the aluminum alloy foil among the 10 samples was Amm, the number of samples having pinholes or the like formed in the shallowest molding depth at which pinholes or the like were formed in the aluminum alloy foil was B, and the value calculated by the following equation was rounded off at the 2 th position after the decimal point to obtain the limit molding depth of the outer packaging material for electricity storage devices. The results are shown in Table 1.
Ultimate forming depth of Amm + (0.5 mm/10) × (10-B)
[ Table 1]
The aging conditions of comparative examples 1 and 2 shown in table 1 mean conditions of aging treatment (standing at 60 ℃ for 24 hours and then at 80 ℃ for 24 hours) performed after laminating the adhesive layer on the barrier layer having the corrosion-resistant film and the 2-axis stretched nylon film side of the base material layer, since the layer corresponding to the first adhesive layer is not present in comparative examples 1 and 2.
The exterior materials for electricity storage device of examples 1 to 10 were each composed of a laminate comprising at least a first base material layer, a first adhesive layer, a second base material layer, a second adhesive layer, a barrier layer, and a heat-fusible resin layer in this order, wherein at least one surface of the barrier layer was provided with a corrosion-resistant coating, and when the corrosion-resistant coating was analyzed by time-of-flight secondary ion mass spectrometry, the corrosion-resistant coating was derived from PO3 -Peak intensity P ofPO3Relative to that derived from CrPO4 -Peak intensity P ofCrPO4Ratio PPO3/CrPO4In the range of 6 to 120Within the range. As is clear from the results shown in table 1, the outer packaging materials for electricity storage devices of examples 1 to 10 can maintain high adhesion of the barrier layer having the corrosion-resistant coating film even when the electrolyte adheres thereto, and have excellent moldability. Of these, the outer covering materials for electricity storage device of examples 1 to 5 and 8 to 10 had particularly high moldability because the first adhesive layer and the second adhesive layer were set to have a hardness of 20MPa or more.
In contrast, in comparative example 1, the peak intensity ratio PPO3/CrPO4When the thickness is less than 6, the initial adhesion and the adhesion after the electrolyte immersion are inferior to those of examples, and the ultimate molding depth is less than 7.5mm, which results in inferior moldability to those of examples.
In comparative example 2, the peak intensity ratio PPO3/CrPO4When the thickness exceeds 120, the adhesiveness after the immersion in the electrolyte solution is inferior to that of example, and the ultimate molding depth is less than 7.5mm, which is inferior to that of example.
As described above, the present invention provides inventions of the embodiments disclosed below.
Item 1. an exterior material for an electricity storage device, which comprises a laminate comprising at least a first base material layer, a first adhesive layer, a second base material layer, a second adhesive layer, a barrier layer and a heat-fusible resin layer in this order,
a corrosion-resistant coating film on at least one surface of the barrier layer,
when the corrosion-resistant coating is analyzed by time-of-flight secondary ion mass spectrometry, the corrosion-resistant coating is derived from PO3 -Peak intensity P ofPO3Relative to that derived from CrPO4 -Peak intensity P ofCrPO4Ratio PPO3/CrPO4In the range of 6 to 120.
Item 2. the outer packaging material for an electric storage device according to item 1, wherein,
the hardness of the first adhesive layer as measured by nanoindentation is 20MPa or more, and,
the hardness of the second adhesive layer as measured by the nanoindentation method is 20MPa or more.
the first base material layer contains at least one of polyamide and polyester,
the second base material layer contains polyamide.
The outer packaging material for an electricity storage device according to any one of the above 1 to 3, wherein,
the corrosion-resistant film is provided on at least the surface of the barrier layer on the side of the heat-fusible resin layer,
the corrosion-resistant film and the heat-fusible resin layer are laminated via an adhesive layer.
the resin constituting the adhesive layer has a polyolefin skeleton.
Item 6 the outer packaging material for an electric storage device according to item 4 or 5, wherein,
the adhesive layer contains an acid-modified polyolefin.
The outer packaging material for an electric storage device according to any one of items 4 to 6, wherein,
when the adhesive layer was analyzed by infrared spectroscopy, a peak derived from maleic anhydride was detected.
Item 8 the outer packaging material for an electric storage device according to item 6, wherein,
the acid-modified polyolefin of the adhesive layer is maleic anhydride-modified polypropylene,
the heat-fusible resin layer contains polypropylene.
Item 9. A method for producing an outer packaging material for an electricity storage device, comprising a step of laminating at least a first base material layer, a first adhesive layer, a second base material layer, a second adhesive layer, a barrier layer, and a heat-fusible resin layer in this order to obtain a laminate,
a corrosion-resistant coating film on at least one surface of the barrier layer when the barrier layer is laminated,
the corrosion-resistant coating is subjected to a time-of-flight secondary ion mass spectrometryIn the case of analysis, derived from PO3 -Peak intensity P ofPO3Relative to that derived from CrPO4 -Peak intensity P ofCrPO4Ratio PPO3/CrPO4In the range of 6 to 120.
an electricity storage device element including at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the outer packaging material for an electricity storage device according to any one of items 1 to 8.
Description of the symbols
10 outer packaging material for electricity storage device
11 first base material layer
12 second substrate layer
21 first adhesive layer
22 second adhesive layer
3 Barrier layer
4 Heat-fusible resin layer
5 adhesive layer
6 surface coating
Claims (10)
1. An outer packaging material for an electricity storage device, characterized in that:
comprising a laminate comprising at least a first base material layer, a first adhesive layer, a second base material layer, a second adhesive layer, a barrier layer and a heat-sealable resin layer in this order,
a corrosion-resistant coating film is formed on at least one surface of the barrier layer,
in the case of analyzing the corrosion-resistant coating by time-of-flight secondary ion mass spectrometry, the source is PO3 -Peak intensity P ofPO3Relative to that derived from CrPO4 -Peak intensity P ofCrPO4Ratio PPO3/CrPO4In the range of 6 to 120.
2. The outer packaging material for an electricity storage device according to claim 1, characterized in that:
the first adhesive layer has a hardness of 20MPa or more as measured by a nanoindentation method,
the hardness of the second adhesive layer measured by a nanoindentation method is 20MPa or more.
3. The outer packaging material for an electricity storage device according to claim 1 or 2, characterized in that:
the first substrate layer contains at least one of polyamide and polyester,
the second substrate layer contains polyamide.
4. The exterior material for an electricity storage device according to any one of claims 1 to 3, characterized in that:
the corrosion-resistant film is provided on at least the surface of the barrier layer on the side of the heat-fusible resin layer,
the corrosion-resistant film and the heat-fusible resin layer are laminated via an adhesive layer.
5. The outer packaging material for an electricity storage device according to claim 4, characterized in that:
the resin constituting the adhesive layer has a polyolefin skeleton.
6. The outer packaging material for an electricity storage device according to claim 4 or 5, characterized in that:
the adhesive layer contains an acid-modified polyolefin.
7. The exterior material for an electricity storage device according to any one of claims 4 to 6, characterized in that:
when the adhesive layer was analyzed by infrared spectroscopy, a peak derived from maleic anhydride was detected.
8. The outer packaging material for an electricity storage device according to claim 6, characterized in that:
the acid-modified polyolefin of the adhesive layer is maleic anhydride-modified polypropylene,
the heat-fusible resin layer contains polypropylene.
9. A method for manufacturing an outer packaging material for an electricity storage device, characterized by comprising:
comprises a step of laminating at least a first base material layer, a first adhesive layer, a second base material layer, a second adhesive layer, a barrier layer and a heat-fusible resin layer in this order to obtain a laminate,
a barrier layer having a corrosion-resistant coating film on at least one surface thereof when the barrier layer is laminated,
in the case of analyzing the corrosion-resistant coating by time-of-flight secondary ion mass spectrometry, the source is PO3 -Peak intensity P ofPO3Relative to that derived from CrPO4 -Peak intensity P ofCrPO4Ratio PPO3/CrPO4In the range of 6 to 120.
10. An electricity storage device characterized in that:
an electric storage device element including at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the outer packaging material for an electric storage device according to any one of claims 1 to 8.
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| JP2019009813 | 2019-01-23 | ||
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| PCT/JP2020/002427 WO2020153459A1 (en) | 2019-01-23 | 2020-01-23 | Exterior material for power storage device, method for manufacturing exterior material for power storage device, and power storage device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108701780A (en) * | 2016-11-28 | 2018-10-23 | 大日本印刷株式会社 | Battery use packing material, its manufacturing method and battery |
| CN108886116A (en) * | 2016-04-12 | 2018-11-23 | 大日本印刷株式会社 | Battery use packing material, its manufacturing method and battery |
| CN108886112A (en) * | 2016-11-28 | 2018-11-23 | 大日本印刷株式会社 | Battery use packing material, the manufacturing method of battery use packing material and battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4668379B2 (en) * | 1999-12-17 | 2011-04-13 | 大日本印刷株式会社 | Method for producing polymer battery packaging material |
| JP2003247079A (en) * | 2002-02-20 | 2003-09-05 | Dainippon Printing Co Ltd | Nickel member for battery, battery obtained by using the same and covering material therefor |
| JP6136382B2 (en) * | 2013-03-07 | 2017-05-31 | 油化電子株式会社 | Method for producing laminated film for battery exterior |
| US20180312943A1 (en) * | 2015-10-28 | 2018-11-01 | Dai Nippon Printing Co., Ltd. | Battery packaging material, battery, method for producing battery packaging material, and aluminum alloy foil |
| WO2019017457A1 (en) * | 2017-07-19 | 2019-01-24 | 大日本印刷株式会社 | Battery wrapping material, method for producing battery wrapping material, and battery |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108886116A (en) * | 2016-04-12 | 2018-11-23 | 大日本印刷株式会社 | Battery use packing material, its manufacturing method and battery |
| CN108701780A (en) * | 2016-11-28 | 2018-10-23 | 大日本印刷株式会社 | Battery use packing material, its manufacturing method and battery |
| CN108886112A (en) * | 2016-11-28 | 2018-11-23 | 大日本印刷株式会社 | Battery use packing material, the manufacturing method of battery use packing material and battery |
Non-Patent Citations (2)
| Title |
|---|
| 刘继福;郭纯武;刘嘉鑫;: "聚合物锂电池软包装材料的瓶颈突破" * |
| 章结兵;石亚丽;韩梓涛;: "软包锂离子电池封装铝塑膜材料保护机理分析及其测试方法" * |
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| WO2020153459A1 (en) | 2020-07-30 |
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